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Structures and Magnetic Properties of Manganese(II) Compounds Based on Chains with Simultaneous Carboxylate and Pseudohalide Bridges



Various zwitterionic carboxylate ligands form MnII coordination polymers with carboxylate and pseudo-halide bridges mixed in different ways. With mono-zwitterions, [Mn(N3)2(L1)(H2O)]n and [Mn(N3)2(L2)]n contains 1D chains with (μ-1,1-N3)(μ-1,3-OCO) and (μ-1,1-N3)2(μ-1,3-OCO) bridges, respectively. With di-zwitterions, [Mn(N3)(L3)]n(ClO4)n forms a 2D network based on chains with (μ-1,1-N3)(μ-1,3-OCO)2 bridges, whereas [Mn2(X)4(L4)]n·2nH2O (X = N3 or NCO) are interpenetrating 3D networks based on chains with (μ-1,1-X)2(μ-1,3-OCO) bridges. With a tri-zwitterion, [Mn7(N3)14(OH)2(L5)(H2O)6]n·4nH2O is a 2D network based on a novel chain in which μ-1,1-N3- and μ-1,3-OCO-bridged trinuclear motifs and μ3-OH- and μ-1,1-N3-bridged tetranuclear motifs are linked by μ-1,3-N3 and μ3-1,1,3-N3. All compounds exhibit antiferromagnetic interactions, the magnitude of which depends upon the nature and mixing mode of the bridges, and follow the trend (μ-N3)(μ-OCO) < (μ-N3)(μ-OCO)2 < (μ-N3)2(μ-OCO) < (μ-NCO)2(μ-OCO).

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